Investigation of linear and nonlinear Raman scattering for isotopologues of Ru(bpy) 3 2+

Daniel W. Silverstein, Chris B. Milojevich, Jon P. Camden, Lasse Jensen

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Tris(2,2′-bipyridine)ruthenium(II), Rubpy, an important transition metal complex for its robust photochemistry, is studied using simulated resonance Raman scattering (RRS) and resonance hyper-Raman scattering (RHRS) in comparison to measured surface-enhanced Raman scattering (SERS) and surface-enhanced hyper-Raman scattering (SEHRS). Detailed examination of the simulated data shows that many of the observed features in the experiments are captured by the theory. For the metal-to-ligand charge transfer (MLCT) absorption band at 452 nm, it is demonstrated that the shoulder on the absorption band at 425 nm is not a vibronic feature and that the line shape should be considered as coming from two separate MLCT states. We find that good agreement can be obtained by comparing simulated spectra to the SERS and SEHRS spectra on resonance with the absorption band. However, the simulations do not capture the high sensitivity of relative peak intensities observed during wavelength scanned SERS and SEHRS experiments. This result is interpreted on the basis of discussion of the literature and the approximations made in the vibronic model, where it is concluded that the simulations underestimate interference effects. These results demonstrate the complexity of using theoretical methods for accurately describing the electronic structure of large molecules, and that commonly used exchange-correlation functionals like B3LYP and LC-PBE cannot completely describe all of the vibronic features in the Raman scattering of Rubpy.

Original languageEnglish (US)
Pages (from-to)20855-20866
Number of pages12
JournalJournal of Physical Chemistry C
Volume117
Issue number40
DOIs
StatePublished - Oct 10 2013

Fingerprint

Raman scattering
Raman spectra
Absorption spectra
absorption spectra
Charge transfer
Metals
Ligands
charge transfer
tris(2,2'-bipyridine)ruthenium II
ligands
Ruthenium
Photochemical reactions
Coordination Complexes
resonance scattering
shoulders
Metal complexes
functionals
photochemical reactions
metals
ruthenium

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Silverstein, Daniel W. ; Milojevich, Chris B. ; Camden, Jon P. ; Jensen, Lasse. / Investigation of linear and nonlinear Raman scattering for isotopologues of Ru(bpy) 3 2+. In: Journal of Physical Chemistry C. 2013 ; Vol. 117, No. 40. pp. 20855-20866.
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Investigation of linear and nonlinear Raman scattering for isotopologues of Ru(bpy) 3 2+. / Silverstein, Daniel W.; Milojevich, Chris B.; Camden, Jon P.; Jensen, Lasse.

In: Journal of Physical Chemistry C, Vol. 117, No. 40, 10.10.2013, p. 20855-20866.

Research output: Contribution to journalArticle

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